Concentration of sylvinite ores



Patented Dec. 26, 1944 CONCENTRATION OF SYLVINITE ORES Allen T. Cole, Lakeland, Fla" assignor to Minerals Separation North American Corporation, New York, N. Y., a corporation of Maryland No Drawing. Application May 15, 1943, Serial No. 487,147

23 Claims.

This invention relates to the concentrating, or separation of the values from soluble ores. More particularly, it relates to the separation of sylvite (potassium chloride, KCl) from sylvinite ores such as, for example, those found in the Carlsbad district of New Mexico.

The invention resides in improved methods of effecting the separation of the desired sylvite from such ores by froth flotation, skin flotation, agglomeration tabling and other methods involving wet stratification with the use of appropriate agents which effect the separation of the sylvite from the other ore constituents.

It is already known that sylvite can be recovered from a saturated solution of the soluble constituents of sylvinite ore in accordance with well-established concentration operations by using as a collector an aliphatic amine containing a straight chain hydrocarbon group of at least 7 carbon atoms, or the salts of such amines resulting from their combination with water-soluble acids.

The general objects of the present invention are to produce concentrates of the. desired sylvite which are of high commercial grade, with high percentages of recovery, with economy in the use of reagents and with reliable and easily controlled operation of the plant. These objects are attained by the processes embodying the present invention which are hereinafter described.

The rnethods of the present invention are the result of the discovery that greatly improved results, as to grade and recovery of the desired sylvite and as to control of operations, can be obtained by the use as auxiliary agents, in conjunction with the aforesaid straight chain alkyl amines used as collectors, of all those proteinaceous protective colloids which are either water soluble or colloidally clispersible.

The straight chain alkyl amines useful as collectors for sylvite, the action of which is improved by the concurrent use as auxiliary agents of proteinaceous protective colloids, include the following aliphatic primary amines: n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, ntetradecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, and n-octadecenylamine. The lower members of this series may be added to the ore pulp in the form of the free base or as the salts formed by their combination with acids which are themselves relatively devoid of surface active properties, such, for example, as hydrochloric acid, nitric acid, acetic acid, etc. The higher members of the alkyl amines, being much less soluble, are generally used in the form of their more soluble salts.

These amine collectors may be used individually Or as mixtures. The mixtures need not necessarily consist only of alpihatic primary amines or their salts but may also contain varying proportions of aliphatic secondary and tertiary' amines or their salts, such as are commonly found in commercial products. For example, the

mono-hexadecylamine acetate, together with small quantities of secondary and tertiary amine acetates. Another suitable commercial product is that sold by E. I. du Pont De Nemours 8: Company, Inc., as "D. P. 243 which is a aqueous paste of technical laurylamine hydrochloride understood to contain approximately 18% octylamine hydrochloride, 10% decylamine hydrochloride, laurylamine hydrochloride, 17% myristylamine hydrochloride, and traces of secondary and tertiary amines. Another collector, which may be made from a commercial product, is castor amine acetate prepared by neutralizing with acetic acid the product sold by National Oil Products Company under the name Nopco CVU (castor amine). The castor amine acetate is an example of a straight chain alkyl amine collector which is not economically useful by itself, because of poor recovery, but which is rendered useful by the conjoint use of auxiliary agents, as hereinafter described.

Research done on large numbers of protein type substances, their derivatives and degradation products has resulted in the discovery that those proteinaceous substances which belong to the class of protective colloids are useful as auxiliary agents for the purposes hereinabove stated.

-I. Simple proteins:

a. Albumins (albumin) b. Globulins (edestin) c. Glutelins d. Prolamines e. Albuminoids (collagen) I. Histones g. Protamines II. Compound or conjugated proteins:

. Chromoproteins (hemoglobin) Glycoor glucoproteins (mucin) Phosphorproteins (casein) Nucleoproteins Lecithoproteins Lipoproteins The derived proteins are not herein considered to be a distinct class of proteins, although often so classified, but are considered as members of the class from which derived. The simple proteins include all proteins which, on being treated with enzymes or acids, break-up only into amino-acids or their derivatives. The conjugated proteins are considered as compounds of simple proteins with some other non-protein group. Included as proteins, within the intent of this invention, are also all of the derivatives of simple and conjugated proteins including their decomposition, degradation and hydrolysis products together with all synthetic compounds similar in structure and function.

This invention relates more particularly to the use, as auxiliary agents, of those proteins and protein decomposition, degradation and hydrolysis products which function as protective colloids. The better known materials in this class of proteinaceous protective colloids are gelatin, isinglass, casein, albumin, glue, protalbinlc and lysalbinic acids, proteoses, peptones, blood proteins, mucin and edestin. The members of this class may be naturally occurring substances in plant and animal tissues, complex mixtures or specific chemical compounds isolated from such tissues, or synthetic chemical compounds similar in structure and function to the naturally occurring substances.

Collagen, a member of the class of albuminoids, is the chief constituent of connective tissue and represents about 75% by weight, on the dry basis, of the corium and 33% of the bones of animals. Both glue and gelatin are formed by the hydolysis of collagen, and whether the product is called glue" or gelatin depends upon the degree of the hydrolysis andthe purity of the raw material.

Commercially gelatin is prepared from skins, bones, and the by-products of the slaughterhouses and butcher shops. These wastes are first treated with steam under pressure to remove the fats and greases after which they are digested in dilute acid to remove the mineral matter. The collagen thus obtained is called ossein. The ossein is then digested with slaked lime and water, and after aging properly the gelatin is extracted with warm water. The process is essentially the same in the manufacture of animal glue except that less care is used in selecting the raw material. Fish glue, which has been found very effective as an auxiliary agent, is made from the skins of the cod, cusk and other fish. Isinglass is the dry glue made by boiling the air-bladder of the sturgeon. The term'g1ue," as used herein and in the claims is to be construed as including gelatin and those glues specifically referred to above and similar adhesive materials of a proteinaceous protective colloid nature, which may be naturally occurring substances in plant and animal tissues, compl'ex mixtures or specific chemical components isolated from such tissues, or synthetic chemical compounds similar in structure and function to the naturally occurring substances. Gelatin, which is essentially an unhydrolyzed glue is, for the purposes of the present invention, not distinguishable from glue and is to be considered as its full equivalent.

The phosphorus containing proteinaceous protective colloids include the class of phosphoproteins, the class of lecithoproteins (including liproproteins), and the class of nucleoproteins. Members of the class of phosphoproteins and the aseasos class of lecithoproteins have been found to function effectively as auxiliary agents. Casein, a member of the class of phosphoproteins, may be precipitated from milk on theaddition of lactic or acetic acid or rennet. It may also be obtained from blood, the seeds of various cereal plants, and soybeans. It represents about 10- 20% of the gluten of flour. The soluble casein derivatives, for example ammonium caseinate, have been found to function effectively as auxiliary agents. Lecithin, a phosphorus-containing protein, is a fatty acid ester of a monoamino-monophosphatide occurring in various animal and vegetable tissues an egg yolk. A commercial lecithin of vegetable origin known as Yelkin ST has been successfully used as an auxiliary agent.

Useful auxiliary agents of the protective collaid class also result when bones, together with the adhering tissue such as cartilage, muscle and fat, are destructively distilled. The distillate, bone oil, contains a wide variety of protein degradation products and probably products which have resulted from the recombination of some of the simpler constituents. In some cases it is desirable to remove, preferably by distillation, some of the low boiling constituents which are not members of the class of protective colloids.

Other examples are edestin, which occurs in hemp seeds, and albumin, a protein found in the white of eggs, in blood and in many other animal and vegetable tissues. Good results have been obtained with a digested (causticized) protein material produced by the A. E. Staley Mfg. Co. as .a by-product in the manufacture of starch. As an example of a synthetic material, successful use has been made of the reaction products of higher fatty acid chlorides and protein cleavage products containing protalbinic and lysalbinic acids. Such a product is that sold under the trade name "Lamepon" by Chemical Marketing Co., Inc.

The mention of specific materials or their sources or methods of production is purely for purposes of illustration and it is within the scope of the invention to use as auxiliary agents with amine collectors in the concentration of sylvite any proteinaceous material which belongs in the class of protective colloids and which is either soluble or colloidally dispersible in an aqueous pulp or solution.

The following specific examples of embodiments of the invention show, by comparison with the Comparative Tests in which no proteinaceous protective colloid was used, the advantages to be obtained from the use of these compounds as auxiliary agents.

In practicing the methods of the present inevention, desliming of the sylvinite ore is desirable; and it is also sometimes desirable to add a frothing agent, such as pine oil, in addition to the collector and the auxiliary agent, when the desired mineral is to be concentrated by froth flotation, or a petroleum. oil such as fuel oil when concentration is to be effected by tabling.

Comparative test A.--Sylvinite ore from Carlsbad, New Mexico, was crushed so that it would pass through a IO-mesh screen, and was then deslimed and ground so that it would pass through a 35-mesh screen, after which it was made into a pulp to about 20% solids with a saturated solution of ore constituents. Reagent,

as hereinafter specified, was added to this pulp,.

the pulp was agitated about lo seconds to distribute the reagent and flotation was then effected. The first or rougher froth concentrate was returned to the flotation machine, diluted and refloated. This was repeated on the second froth concentrate. The reject of the first flotation operation was final tailings. Rejects'of the second and third flotation operations were middlings to be returned to the flotation circuit and ffirther values recovered therefrom. The reagents used were Am. Ac. 1180- 1.00 lb. and pine oil 0.2 lb., both per ton of ore treated. The results were as follows:

Per cent Percent KC] Product weight K01 recovery 100. 0 30. 7 100. 0 l5. 93. 5 47. 3 7. 7 90. 6 22. 7 7. 9 58. 4 l5. 0 64. 9 5. 5 l1. 6 4. 0 25. 8 3. 4

Product Percent Percent KCl It will be noted that the use of the casein glue in conjunction with the other reagents, as is shown by comparison of this example with Comparative test A, improved the recovery by 41.6% (88.9% KC] recovery when casein glue was used, as against 47.3% KCl recovery without it) and increased grade slightly by 1.7% (95.2% as against 93.5%):

Example 2.The ore, procedure and reagents were the same as in Example 1 except that instead of casein glue the auxiliary agent was fish glue (Rogers Fish Glue, Rogers Isinglass & Glue Co.) added to the pulp in the form of a aqueous solution. The results were as follows:

Per cent Per cent K01 Pmdm weight KC] recovery Feed 100. 0 27. 4 100. 0 Concentrate 23. 5 95. 7 82. 2 Middling-2 1. 9 76. 9 5. 3 Middling 4. 7 21. 7 3. 7 Tailing 66. 4 3. 3 8. l Slime 3. 5 5. 6 0. 7

weight KCl recovery pulp as a 3% aqueous solution. The results were as follows:

Per cent Per cent KC] Product weight KC] recovery Feed 100.0 28 6 100. 0 Concentrate l8. 9 92. 3 60. 9 Middl 1. 8 79:6 5. 0 4. 2 46. 7 6. 9

By comparison of Example 3 with Comparative test A, it will be seen that the lecithin increased recovery by 13.6% with a slight loss in grade amounting to but 1.2%.

Example 4.The ore, procedureand reagents were the same as in the preceding examples except that the auxiliary agent was digested (causticized) protein material (the product of that designation marketed by A. E. Staley Manufacturing Co.) added to the pulp as a 3% aqueous solution. The results were as follows:

. Per cent Per cent K01 Product weight KC] recovery Feed 100.0 28.9 0 Concentrate g 23. 2 91. 5 73 4 Md 2. 5 77. 8 6 7 5.2 30.0 5 4 64.6 4.9 10 8 4. 5 23. 7 3 7 By comparison of Example 4 with Comparative test A, it will be seen that the addition of the digested protein increased recovery by 26.1%

= with a slight loss in grade of 2%.

Comparattve test B.This test will serve as a basis of comparison for Examples 5, 6 and '7 which follow. The ore, preparation of the feed and procedure were the same as in Comparative test A, except that the 1.00 lb. per ton of ore of "Am. Ac. 1180-C was used as in the preceding test but without the addition of pine oil. The results were as follows:

Per cent Per cent KG] Product weight KC! recovery Example 5.-The ore, procedure and -reagent were the same as in Comparative test B except that 0.8 lb. per ton of ore of ammonium caseinate was used as an auxiliary agent. It was added to the pulp as a 5% aqueous solution of a product of the Casein Company of America sold as Protovac #7631. The results were as By comparison of Example 5 with Comparative test B, it will be seen that the addition of the ammonium caseinate increased recovery by 55.7%

75 and increased grade by 0.4%.

Example 6.'I'he ore, procedure and reagent were the same as in Comparative test B except that 0.8 lb. per ton of ore of gelatin (Eastmans .practical gelatin) was used as an auxiliary agent, added to the pulp as 5% aqueous solution,

. slightly warm. Results were as follows:

' Per cent Per cent KCl Product weight KC] recovery m. 2 100. 93. 8 9o. 2 18. 9 L 6 4. 3 L 4 1 5 5. 7 7. 8 L 1 By comparison of Example 6 with Comparative test B, it will be seen that the addition of gelatin increased recovery by 71.3%; grade remaining practically the same.

Example 7.The ore, procedure and reagent were the same as in Comparative test B except that 0.8 lb. per ton of ore or blood albumin was used as an auxiliary agent.. The blood albumin was made up to a 5% solution andto each 100 cc. of the solution 1 cc. of 5% sodium hydroxide solution was added. The results were as follows:

namely DuPonts DP-243," in the. amount or 1.4 lbs. together with pine 011 0.2 lb., both per ton of ore. The results were as follows:

Per cent Per cent KC] f weight K01 recovery 27. 6 1M. 0 88. 1 88. l 73. 9 V 17. 4 53. 8 29. 5

Example 9.The ore, procedure and. reagents were the same as in Comparative test D except that 0.8 lb. per ton of ore of bone oil was added as an auxiliary agent. The results were as follows:

Per cent Per cent KC K01 Product weight KC] recovery recovery M. 6 100. 0 100. 0 03. 3 84. 6 48. 2 26. 8 3. 3 l0. 8 6. 2 2. 8 17. 9 3. 0' 8. 3 I). 3 19. 0' l. 1 2. 9

By comparison of Example '1 with Comparative test A, it will be seen that the addition of the blood albumin increased recovery by 65.6% while grade decreased only 0.4%.

Comparative test C.This test will serve as a basis of comparison for Example 8 and illustrates the beneficial effects of the auxiliary agent in conjunction with a different collector than that used in the preceding examples and comparative tests. The ore, preparation of the feed and procedure were the same as in the preceding examples. The reagents were 3 lbs. of castor amine acetate, made as heretofore described and used as a 5% solution, and 0.2 lb. of pine oil, both per ton of ore. The results were as follows:

Per cent Per cent KC! Product weight K01 recovery Per cent Per cent KO] mm weight K01 recovery 32.4 moo no use Example 10.-The ore, procedure and reagent were the same as in Comparative test E except that 0.8 lb. per ton of ore of ammonium caseinate, added to the pulp as a 3% aqueous solution, was used as an auxiliary agent. The results were as follows:

Per cent Per cent KC] Pmduc" weight K 1 recovery Comparison of Example 10 with Comparative test E shows that the recovery was increased, by the addition ofammonium caseinate, by 18.5% and grade was increased by 0.7%.

Comparative test F.-'I'his test will serve as a basis of comparison for Example 11, and these two tests are also illustrative of the beneficial result obtained from the use of an auxiliary agent of the invention when a concentration procedure different from that used in all of the foregoing examples is used. Table concentration methods were used in these two tests. The ore was from the same source as that used in the preceding examples and was first reduced to particle sizes ranging from about minus 6 to about plus 35 mesh and then partially deslimed. It was then made up to a pulp in which the ratio of brine to ore was 1:1.88 by weight and conditioned with the reagent for about one minute. The sole reagent was Am. Ac. 1180-C 0.5 lb. per ton of ore The conditioned pulp was fed to a shaking table with a saturated aqueous solution of soluble ore constituents. The sylvite concentrate was recovered at the side of the table and the rejected constituents went oil! at the end of the table. The results were as follows:

Example 11.The ore, procedure and reagent were the same as in Comparative test F except that 0.4 lb. per ton of ore of glue (Rogers fish glue) was added as an auxiliary agent as a 5% aqueous solution. The results were as follows:

Per cent Per cent KCl f weight x01 recovery 25.0 01 7 sac as as 1.4

By comparison of Example 11 with Comparative test F, it will be seen that recovery was increased 34.3% while grade decreased only 2.5%.

Comparative test G.This test will serve as a basis of comparison for Example 12; and these two tests are also illustrative of the beneficial result obtained from the use of a glycoprotein as an auxiliary agent. A sample of sylvinite ore ground to pass through a 28-mesh screen was deslimed and then ground to pass a 35-mesh screen, after which it was made into a pulp to about 20% solids, conditioned with reagents for seconds and subjected to froth flotation as explained in Comparative test A. The reagent used in this test was Du Pont's DP-243, in the amount of 0.9 lb. per ton of ore. The results were as follows:

Ezari'zple 12.-The ore, procedure and reagent were the same as in Comparative test G except that 1.3 lbs. per ton of ore of mucin (Armour and Companys concentrated gastric mucin) was addedas an auxiliary agent as a 5% aqueous dispersion. The results were as follows:

Per cent Per cent K01 Pmduct weight K01 recovery By comparison of Example 12-with Comparative test G, it will be seen that recovery was increased 35.0% and grade was increased 3.2% by the use of mucin as an auxiliary agent.

It is to be understood that the foregoing examples, are merely illustrative of the present invention and that, within the scope of the appended claims, the invention may be practiced otherwise than as specifically illustrated and described.

What is claimed is:

1. The improvement in the method of separating sylvite from a pulp containing it which comprises subjecting said pulp to a concentrating process employing a collector selected from the group consisting of aliphatic amines containing a straight chain hydrocarbon group of at least 7 carbon atoms and their soluble salts formed by their. combination with acids which are relatively devoid of surface active properties, which resides in distributing in said pulp a useful amount of an auxiliary agent selected from the class consisting of the water-soluble and colloidally dispersible proteinaceous protective colloids, and thereafter subjecting the pulp to a separation treatment to remove the desired sylvite.

2. A method as set forth in claim 1, wherein the pulp is formed from sylvinite ore and a substantially saturated aqueous solution of the soluble ore. constituents.

3. A method as set forth in claim 1, wherein the sylvinite ore is substantially deslimed before the collector and the auxiliary agent are added.

4. A method as set forth inclaim 1, wherein the separation treatment is a froth-flotation treatment in a froth-flotation machine.

5. A method as set forth in claim 1, whereinthe separation treatment is by means of a shaking table.

6. A method as set forth 'in claim 1, wherein a frothing agent is used in conjunction with the collector and auxiliary agent and the separation of the sylvite is effected by froth flotation.

' 7. A method as set forth in claim 1, wherein a petroleum oil is used in conjunction with the collector and auxiliary agent, the sylvite agglomerated and the agglomerates separated.

8. A method as set forth in claim 1, wherein the auxiliary agent is a proteinaceous animal derivative having the properties of a protective colloid.

9. A method as set forth in claim 1, wherein the auxiliary'agent is a proteinaceous vegetable derivative having the properties of a protective colloid.

10. A method as set forth in claim 1, wherein the auxiliary agent is a hydrolytlc product of collagen.

11. A method as set forth in claim 1, wherein the auxiliary agent is an albuminoid.

12. A method as set forth in claim 1, wherein the proteinaceous colloid is glue.

13. A method as set forth in claim 1, wherein the auxiliary agent is an albumin.

14. A method as set forth in claim 1, wherein the auxiliary agent is blood albumin.

15. A method as set forth in claim 1, wherein the auxiliary agent is a phosphorus containing proteinaceous protective colloid.

16. A method as set forth in claim 1, wherein the auxiliary agent is a water-soluble casein derivative. ,1

17. A method as set forth in claim 1, wherein the auxiliary agent is a soluble-casein salt.

18. A method as set forth in claim 1, wherein the auxiliary agent is ammonium caseinate.

20. A method as set-forth in claim 1, wherein castor amine acetate is used as the collector.

21. A method as set forth in claim 1, wherein laurylamine hydrochloride is used as the collector.

22. A method as set forth in claim 1, wherein octadecylamine acetate is usedas the collector in conjunction with a frothing agent and separation is eifected by froth-flotation to remove the sylvite.

23. A method as set forth in claim 1, wherein octadecylamine acetate is used as the collector in. conjunction with a petroleum oil and separation is effected by agglomeration tabllng treat- 19. A method as set forth in claim 1, wherein i5 ment to remove the sylvite;

octadecylamine acetate is used as the collector.

- ALLEN T. COLE. 

